JP5217150B2 - Resin composition and use thereof - Google Patents

Description

  The present invention relates to a cyclic olefin-based ring-opening copolymer composition containing an imide compound capable of controlling the refractive index anisotropy, a film or stretched film obtained from the resin composition, its use, and the resin composition Relates to an optical component obtained from the above. Specifically, the present invention relates to a cyclic olefin-based resin composition having excellent transparency, heat resistance, solubility in an organic solvent, strength and processability, and having specific birefringence and wavelength dependency, and uses thereof.

  Since the cyclic olefin resin generally has a relatively small birefringence, its use for a polarizing plate protective film, a liquid crystal substrate material, an optical disk, various optical lenses, an optical fiber and the like has been studied recently. In addition, since the cyclic olefin resin exhibits appropriate birefringence by controlling the processing conditions, an optical compensation film actively utilizing this is actually used. For example, Patent Documents 1 to 4 describe retardation plates using a cyclic olefin-based resin film. Patent Documents 5 to 7 describe the use of a cyclic olefin resin film as a protective film for a polarizing plate. Furthermore, Patent Document 8 describes a liquid crystal display element substrate made of a film of a cyclic olefin resin.

  In general, a retardation film is given a function of imparting a retardation (birefringence) to transmitted light by stretching orientation. However, in many resin films, the level of transmitted light increases as the wavelength of transmitted light becomes longer. Since the absolute value of the phase difference (birefringence) tends to be small, it is very difficult to give the transmitted light a specific phase difference such as 1 / 4λ in the entire visible light region (400 to 800 nm). . However, at present, in applications such as reflective and transflective liquid crystal displays and optical disk pickups, a phase difference of ¼λ is actually obtained in a wide wavelength range such as the entire visible light range (400 to 800 nm). On the other hand, a retardation film having a larger positive wavelength dispersion than a cyclic olefin ring-opening (co) polymer currently widely used as a retardation film is required. ing. Polycarbonate is well known as a retardation film having a large positive wavelength dispersion, but such a retardation film is not practical because of its large photoelastic coefficient, and like a cyclic olefin ring-opening (co) polymer. In addition to the small photoelastic coefficient, the development of materials with highly controlled wavelength dispersion is strongly desired. In addition to this, development of resins having various optical characteristics such as positive / negative of birefringence value, magnitude of absolute value thereof, and magnitude of wavelength dependence of phase difference is desired in response to various demands. .

  For this reason, the conventional optical film made of a cyclic olefin resin cannot meet the above-mentioned high demand, and in order to achieve such optical characteristics, a plurality of films are laminated or various kinds of optical characteristics are improved for improving the optical characteristics. A coating agent is applied, or a plurality of stretched films are bonded together with orientation directions to obtain desired optical characteristics. However, the optical film obtained by such a method has problems such as high cost, low yield, and difficulty in reducing the film thickness because of complicated manufacturing processes such as cutting, film bonding, and adhesion.

Under such circumstances, the realization of a single-layer optical film having a desired retardation in a wide wavelength region is desired, and the appearance of a resin capable of producing such an optical film is strongly demanded. .
JP-A-4-245202 JP-A-4-36120 JP-A-5-2108 Japanese Patent Laid-Open No. 5-64865 Japanese Patent Laid-Open No. 5-212828 JP-A-6-511117 JP-A-7-77608 JP-A-5-61026

  The present invention provides a cyclic olefin-based ring-opening copolymer that is excellent in transparency, heat resistance, solubility in organic solvents, strength, and processability, and that can produce an optical component having a wavelength dependency of specific birefringence. It is an object of the present invention to provide a resin composition containing the above, a film obtained therefrom, an optical component, and use thereof.

  As a result of intensive studies by the present inventor, it has been found that a resin composition comprising a compound containing an imide group and a cyclic olefin-based (co) polymer can achieve the above-mentioned problems, and based on this, the present invention is completed. It came.

The resin composition of the present invention is
(A) a cyclic olefin resin having a structural unit represented by the following formula (1);
(B) A polymer having a structural unit represented by the following formula (2-1) (hereinafter also referred to as “polymer (2-1)”), and the following formula (2-2) or the following formula (2) -3) (hereinafter, also referred to as “compound (2-2)” and “compound (2-3)”), respectively, containing one or more imide bond-containing compounds selected from the group consisting of It is characterized by.

(In formula (1), a and b are independently 0 or 1, c and d are each independently an integer of 0 to 2. X is a group represented by the formula: —CH═CH— or a formula: A group represented by —CH ₂ CH ₂ —, wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are each independently hydrogen; atom; a halogen atom; an oxygen atom, a sulfur atom, a nitrogen atom or a linking group containing a silicon atom hydrocarbon group which may substituted or unsubstituted 1 to 30 carbon atoms; represents an or polar groups .R ⁷ And R ⁸ , or R ⁹ and R ¹⁰ may be integrated to form a divalent hydrocarbon group, and R ⁷ or R ⁸ and R ⁹ or R ¹⁰ are bonded to each other and bonded to each other. Carbocycle or heterocycle together with carbon atoms (these carbocycles or heterocycles may be monocyclic structures, or other rings may be condensed to form a polycyclic structure) May be.) May be formed.)

(In Formula (2-1), Formula (2-2), and Formula (2-3), A represents a tetravalent organic group, and B, R ¹³ , and R ¹⁴ are each independently a divalent organic group. R ¹¹ and R ¹² each independently represents a monovalent organic group.)
In the resin composition of the present invention, the cyclic olefin resin (A) is a group in which X in the formula (1) is represented by —CH ₂ CH ₂ — among the structural units represented by the formula (1). It is preferable that 90% or more of the structural unit is included.

  Moreover, in the resin composition of this invention, the ratio ((A) / (B)) of cyclic olefin resin (A) and an imide bond containing compound (B) is 99/1-50/50 by weight ratio. It is preferable that it exists in the range.

  The film of the present invention is obtained by forming a film of the resin composition of the present invention by a casting method or an extrusion method. The stretched film of the present invention is obtained by forming the resin composition of the present invention into a film by a casting method or an extrusion method, and heating and stretching the film.

  The polarizing plate of the present invention and the liquid crystal display device of the present invention are characterized by including a stretched film made of the resin composition of the present invention.

  The resin composition according to the present invention can be easily produced by mixing a specific imide bond-containing compound and a cyclic olefin-based ring-opening (co) polymer, and the resulting resin composition is transparent, heat resistant, organic Excellent solubility in solvents, strength, and processability. In addition, the resin composition according to the present invention can freely control the anisotropy of the refractive index and the wavelength dispersion by appropriately adjusting the composition ratio.

  The resin composition according to the present invention is very useful as an optical material, and includes an optical disk, a magneto-optical disk, an optical lens (Fθ lens, pickup lens, laser printer lens, camera lens, etc.), spectacle lens, and optical film / sheet. (Display film, retardation film, polarizing film, polarizing plate protective film, diffusion film, antireflection film, liquid crystal substrate, EL substrate, electronic paper substrate, touch panel substrate, PDP front plate, etc.), transparent conductive film substrate It can be applied to optical materials that require very high-precision optical design, such as optical fibers, light guide plates, optical cards, optical mirrors, ICs, LSIs, and LED sealing materials.

  In particular, the resin composition according to the present invention can be used for an optical film, and is suitable for production of a film formed by a casting method or an extrusion method, and a stretched film obtained by stretching the film. The stretched film is suitable as a retardation film and can be suitably used for applications such as a polarizing plate and a liquid crystal display device.

Hereinafter, the present invention will be specifically described.
In the present specification, the term birefringence is used in the ordinary sense. Further, the value of birefringence (this is referred to as Δn) is a stretched film in which a film formed from a polymer is uniaxially or biaxially stretched and the polymer molecular chains are oriented in one direction. x-axis larger direction) of the draw ratio in biaxial stretching, the in-plane direction perpendicular to the y-axis, the refractive index of the x-axis direction n _x, the refractive index of the Y-axis direction as n _y contrast, the following formula:
Δn = n _x -n _y
The absolute value is different depending on the wavelength of incident light.

And positive (or negative) birefringence means the property of the stretched film when the Δn is positive (or negative).
Next, the phase difference (Retardation, which is referred to as Re) is the following formula:
Re = Δn × d (where d is the optical path length (nm) of transmitted light, and is usually the thickness of the stretched film.)
The absolute value varies depending on the wavelength of incident light.

  The wavelength dependence of the phase difference means the correlation between the value of Re and the wavelength of the incident light. This means that there is a large difference between the value and the absolute value of Re for incident light having a long wavelength. “Positive wavelength dispersion” means that the phase difference becomes smaller as the incident light wavelength becomes longer. “Reverse wavelength dispersion” means that the phase difference becomes longer as the incident light wavelength becomes longer. It means the characteristic that becomes larger.

<Resin composition>
The resin composition of the present invention contains a specific cyclic olefin-based resin (A) and an imide bond-containing compound (B) as essential components. The resin composition of the present invention may be composed only of the cyclic olefin resin (A) and the imide bond-containing compound (B), and may further contain components other than these.

(A) Cyclic olefin resin The cyclic olefin resin (A) used in the present invention is a resin having a structural unit represented by the formula (1) or a composition thereof. In the present invention, the cyclic olefin-based resin (A) may be a polymer composed of a single structural unit represented by the formula (1), and two or more types represented by the formula (1). It may be a copolymer or a mixture comprising structural units, and may be a copolymer having the structural unit represented by the formula (1) and other structural units. Moreover, cyclic olefin resin (A) may contain various additives, such as antioxidant, a light stabilizer, and UV absorber other than the above-mentioned polymer.

Here, a hydrogen atom represented by R ^{1 to} R ¹⁰ in the formula (1); a halogen atom; an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom, which may have a linking group, substituted or non-substituted The substituted hydrocarbon group having 1 to 30 carbon atoms; or the polar group will be described.

As a halogen atom, a fluorine atom, a chlorine atom, and a bromine atom are mentioned, for example.
Examples of the hydrocarbon group having 1 to 30 carbon atoms include alkyl groups such as methyl group, ethyl group and propyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; alkenyl groups such as vinyl group and allyl group; Groups, alkylidene groups such as propylidene groups; aromatic groups such as phenyl groups, naphthyl groups, anthracenyl groups, and the like. A hydrogen atom bonded to a carbon atom in these groups may be substituted with, for example, a halogen atom such as fluorine, chlorine or bromine, a phenylsulfonyl group, a cyano group or the like.

The above substituted or unsubstituted hydrocarbon group may be directly bonded to the ring structure, or may be bonded via a linking group. Examples of the linking group include a divalent hydrocarbon group having 1 to 10 carbon atoms (for example, an alkylene group represented by — (CH ₂ ) _m — (wherein m is an integer of 1 to 10)); A linking group containing an oxygen atom, nitrogen atom, sulfur atom or silicon atom (for example, a carbonyl group (—CO—), a carbonyloxy group (—COO—), a sulfonyl group (—SO ₂ ).
-), sulfonyloxy group (-SO ₂ -O-), an ether bond (-O-), thioether bond (-S-), an imino group (-NH-), amide bond (-NHCO-), siloxane bond ( -Si (R) ₂ O - in) (wherein, R is a methyl group, an alkyl group such as ethyl group); include those continuous I or combinations of two or more are combined.

Examples of polar groups include hydroxyl groups, alkoxy groups having 1 to 10 carbon atoms, alkylcarbonyloxy groups, arylcarbonyloxy groups, alkoxycarbonyl groups, aryloxycarbonyl groups, cyano groups, nitro groups, amide groups, imino groups ( ═NH), triorganosiloxy group, triorganosilyl group, amino group, acyl group, alkoxysilyl group, sulfino group (—SO ₂ H), carboxyl group and the like.

  More specifically, examples of the alkoxy group include methoxy group and ethoxy group; examples of the alkylcarbonyloxy group include acetoxy group and propionyloxy group; and examples of the arylcarbonyloxy group include Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group; examples of the aryloxycarbonyl group include a phenoxycarbonyl group, a naphthyloxycarbonyl group, and a fullyl group. Examples of the triorganosiloxy group include trimethylsiloxy group and triethylsiloxy group; examples of the triorganosilyl group include trimethylsilyl group. Examples of the amino group, for example, primary amino group or the like; group, triethylsilyl group, etc. Examples of the alkoxysilyl group, for example, trimethoxysilyl groups, triethoxysilyl groups, and the like.

R ⁷ or R ⁸ and R ⁹ or R ¹⁰ are bonded to each other to form a carbocyclic or heterocyclic ring (these carbocyclic or heterocyclic rings may have a monocyclic structure, or other rings may be condensed to form A ring structure may be formed).

The cyclic olefin-based resin (A) according to the present invention is not particularly limited, but is gel permeation chromatography (GPC) (GPC measurement condition: measuring instrument; HLC-8220GPC manufactured by Tosoh Corporation, column; Tosoh) Guard column H _XL -H, TSK gel G7000H _XL , 2 TSK gel GMH _XL , TSK gel G2000H _XL are sequentially connected, solvent: tetrahydrofuran, flow rate: 1 mL / min, sample concentration 0.7 to 0.8 wt%, injection 70 μL, measurement temperature: 40 ° C., detector: RI (40 ° C.), standard material: TSK standard polystyrene manufactured by Tosoh Corp.)), the number average molecular weight (Mn) is usually 1000 to 500,000, Preferably it is 2000-300,000, More preferably, it is 5000-300,000, and a weight average molecular weight (Mw) is 5000-2 million normally, Preferably it is 10,000-1 million, More preferably, it is 30,000-500,000 . The logarithmic viscosity measured at a sample concentration of 0.5 g / dL and a temperature of 30 ° C. in chloroform using an Ubbelohde viscometer is 0.4-0.
It is preferably 8 dL / g.

When the logarithmic viscosity (ηinh) is less than 0.4, the number average molecular weight (Mn) is less than 1000, or the weight average molecular weight (Mw) is less than 5000, the cyclic olefin resin (A) In some cases, the strength of the molded product obtained from the resin composition containing selenium decreases significantly. On the other hand, if the logarithmic viscosity (ηinh) is 0.81 or more, the number average molecular weight (Mn) is 500,000 or more, or the weight average molecular weight (Mw) is 2 million or more, the cyclic olefin resin The melt viscosity or solution viscosity of (A) may become too high, and it may be difficult to obtain a desired molded product from the resin composition containing the cyclic olefin resin (A).

Production Method / Monomer of Cyclic Olefin Resin (A) The cyclic olefin resin (A) according to the present invention comprises a cyclic olefin monomer represented by the following general formula (1 ′) as needed. It can be prepared by ring-opening (co) polymerization with other monomers.

(In the formula (1 ′), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ , and a, b, c, and d are respectively (As defined in equation (1))
Specific examples of such cyclic olefin-based monomers include the following.
Bicyclo [2.2.1] hept-2-ene

5-ethylidenebicyclo [2.2.1] hept-2-ene

5-Methylbicyclo [2.2.1] hept-2-ene

5-ethylbicyclo [2.2.1] hept-2-ene

5-Butylbicyclo [2.2.1] hept-2-ene

5-Phenylbicyclo [2.2.1] hept-2-ene

5-Methyl-5-phenylbicyclo [2.2.1] hept-2-ene

5- (Biphenyl-4-yl) bicyclo [2.2.1] hept-2-ene

5- (Naphthalen-2-yl) bicyclo [2.2.1] hept-2-ene

5- (Naphthalen-1-yl) bicyclo [2.2.1] hept-2-ene

5-Cyclohexylbicyclo [2.2.1] hept-2-ene

5- (Cyclohexen-4-yl) bicyclo [2.2.1] hept-2-ene

5-Methoxycarbonylbicyclo [2.2.1] hept-2-ene

5-Ethoxycarbonylbicyclo [2.2.1] hept-2-ene

5-Butoxycarbonylbicyclo [2.2.1] hept-2-ene

5-Cyanobicyclo [2.2.1] hept-2-ene

5-Methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene

5-Methyl-5-ethoxycarbonylbicyclo [2.2.1] hept-2-ene

5-Methyl-5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene

5-Fluorobicyclo [2.2.1] hept-2-ene

5-Trifluoromethylbicyclo [2.2.1] hept-2-ene

Tricyclo [5.2.1.0 ^2,6 ] -8-decene

Tricyclo [5.2.1.0 ^2,6 ] -deca-3,8-diene

Tricyclo [4.4.0.1 ^2,5 ] -3-undecene

7-Methyltricyclo [4.4.0.1 ^2,5 ] -3-undecene

Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

2,10-dimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

2,9-dimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

8-phenyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

8-ethylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

8-phenoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

8- (1-Naphoxy) carbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-
Dodesen

8- (2-Naphoxy) carbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-
Dodesen

8- (4-Phenylphenoxy) carbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10
] -3-Dodecene

8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3
-Dodecene

8-methyl-8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3
-Dodecene

8-methyl-8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10
] -3-Dodecene

8-methyl-8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10
] -3-Dodecene

8-methyl-8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]
-3-dodecene

8-methyl-8-phenoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] −
3-dodecene

8-methyl-8- (1-naphthoxy) carbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

8-methyl-8- (2-naphthoxy) carbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

8-methyl-8- (4-phenylphenoxy) carbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

8-fluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

8-fluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

8-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

8-pentafluoroethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

8,8-difluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

8,9-difluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

8,8-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3
-Dodecene

8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3
-Dodecene

8,8,9-trifluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

8,8,9,9-tetrafluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

8,8,9,9-tetrakis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5
. 1 ^7,10 ] -3-dodecene

8,9-difluoro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene

Pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] -4-pentadecene

Pentacyclo [7.4.0.1 ^2,5 . 1 ^8,11 . 0 ^7,12 ] -3-pentadecene

Pentacyclo [8.4.0.1 ^2,5 . 1 ^9,12 . 0 ^8,13 ] -3-hexadecene

Heptacyclo [8.7.0.1 ^3,6 . 1 ^10,17 . 1 ^12,15 . 0 ^2,7 . 0 ^11,16 ] -4-Eicosen

Heptacyclo [8.8.0.1 ^4,7 . 1 ^11,18 . 1 ^13,16 . 0 ^3,8 . 0 ^12,17 ] -5- ^Henikosen

Spiro [fluorene -9,8'- tricyclo [4.3.0.1 ^2.5] [3] decene

  The cyclic olefin resin (A) used in the present invention can be obtained by ring-opening (co) polymerizing at least one of such norbornene derivatives, but c in the formula (1) is 0. A certain component (A) is preferably used. That is, it is preferable that c in the monomer represented by the formula (1 ′) capable of deriving the cyclic olefin ring-opening polymer represented by the formula (1) is 0. Monomers selected from the cyclic olefin monomers shown are particularly preferred.

  The monomer composition contains, in addition to the cyclic olefin monomer represented by the above formula (1 ′), other copolymerizable monomers as long as the object of the present invention is not impaired. It may be. Examples of the copolymerizable monomer include cyclic olefins such as cyclobutene, cyclopentene, cyclooctene, and cyclododecene; and non-conjugated cyclic polyenes such as 1,4-cyclooctadiene, dicyclopentadiene, and cyclododecatriene. The copolymerizable monomers can be used singly or in combination of two or more. In the present invention, the copolymerizable monomer in the monomer composition is preferably 30 mol% or less, and more preferably 20 mol% or less.

-Ring-opening polymerization catalyst As a catalyst for ring-opening polymerization that can be suitably used for producing the cyclic olefin-based resin (A) according to the present invention, for example,
(I) A catalyst described in Olefin Metathesis and Metathesis Polymerization (KJIVIN, JCMOL, Academic Press 1997) is preferably used. Examples of such a catalyst include (a) at least one selected from compounds of W, Mo, Re, V and Ti, and (b) an alkali metal element (for example, Li, Na, K), alkaline earth. Group metal elements (eg, Mg, Ca), Group 12 elements (eg, Zn, Cd, Hg), Group 13 elements (eg, B, Al), Group 14 elements (eg, Si, Sn, Pd) And a metathesis catalyst comprising a combination with at least one selected from those having at least one of the element-carbon bond or the element-hydrogen bond. In order to enhance the activity of the catalyst, the additive (c) described later may be added.

Specific examples of the component (a) include, for example, WCl ₆ , MoCl ₅ , ReOCl ₃ , VO.
Examples include compounds described in JP-A-1-240517 such as Cl ₃ and TiCl ₄ . These can be used singly or in combination of two or more.

Specific examples of the component (b) include, for example, n-C ₄ H ₉ Li, (C ₂ H ₅ ) ₃ Al, (C ₂ H ₅ ) ₂ AlCl, (C ₂ H ₅ ) _1.5 AlCl _1.5 , ( Examples thereof include compounds described in JP-A-1-240517 such as C ₂ H ₅ ) AlCl ₂ , methylalumoxane, LiH and the like. These can be used singly or in combination of two or more.

  As the additive for the component (c), for example, alcohols, aldehydes, ketones, amines and the like can be preferably used, and further, compounds described in JP-A-1-240517 can be used. Can do. These can be used singly or in combination of two or more.

The amount of the metathesis catalyst formed by combining the above component (a) is such that the molar ratio of “component (a): total monomer” between the component (a) and the total monomer is usually 1 : 500 to 1: 500,000, preferably 1: 1,000 to 1: 100,000. Further, the ratio of the component (a) to the component (b) is such that the metal atom (mole) ratio of “(a) :( b)” is usually 1: 1 to 1:50, preferably 1: 2. It is in the range of ˜1: 30. When the additive (c) is added to the metathesis catalyst, the ratio of the component (a) to the component (c) is such that the molar ratio of “(c) :( a)” is usually 0.005: 1 to The range is 15: 1, preferably 0.05: 1 to 7: 1.

As other catalysts,
(II) A metathesis catalyst composed of a transition metal-carbene complex or a metallacyclobutane complex of Groups 4 to 8 of the periodic table can be used.

Specific examples of the catalyst (II), for example, W (= N-2,6- C 6 H 3 i Pr 2) (= CH t Bu) (O t Bu) 2, Mo (= N-2, 6-C ₆ H ₃ ⁱ Pr ₂ ) (= CH ^t Bu) (O ^t
_{Bu) 2, Ru (= CHCH} = CPh 2) (PPh 3) 2 Cl 2, Ru (= CHPh 2) [P (C 6 H 11) 3] 2 Cl 2 , and the like. These can be used singly or in combination of two or more.

  The amount of the catalyst (II) used is such that the molar ratio of “catalyst (II): total monomer” is usually 1: 500 to 1: 50,000, preferably 1: 100 to 1:10, 000.

The catalysts (I) and (II) may be used in combination.
-Molecular weight regulator The molecular weight of the cyclic olefin-based resin (A) according to the present invention can be adjusted by adjusting the polymerization temperature, the type of catalyst, the type of solvent, etc. It is preferable to adjust by making it coexist in the reaction system of copolymerization. As the molecular weight regulator, for example, ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and other α-olefins and styrene are preferable. Of these, 1-butene and 1-hexene are particularly preferred. These molecular weight regulators can be used singly or in combination of two or more. The amount of the molecular weight regulator used is usually 0.005 to 0.6 mol, preferably 0.02 to 0.5 mol, per mol of all monomers.

-Ring-opening polymerization reaction solvent As a solvent used in the ring-opening polymerization reaction (that is, a solvent that dissolves a monomer, a ring-opening polymerization catalyst, a molecular weight regulator, etc.), for example, pentane, hexane, heptane, octane, nonane, Alkanes such as decane; cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; chlorobutane, bromohexane, methylene chloride, dichloroethane, hexa Halogenated alkanes such as methylene dibromide, chlorobenzene, chloroform, tetrachloroethylene, aryl halides, etc .; saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, iso-butyl acetate, methyl propionate; dibutyl ether , And ethers such as tetrahydrofuran and dimethoxyethane. Among these, aromatic hydrocarbons are preferred. These can be used singly or in combination of two or more. The use amount of the solvent for the ring-opening polymerization reaction is such that the weight ratio of “solvent: total monomer” is usually 1: 1 to 10: 1, preferably 1: 1 to 5: 1. Is desirable.

-Conditions for ring-opening polymerization reaction The reaction initiation temperature for carrying out the ring-opening polymerization reaction is usually 40 to 160 ° C, preferably 45 to 150 ° C, particularly preferably 50 to 140 ° C.

The reaction time for carrying out the ring-opening polymerization reaction is usually 0.1 to 10 hours, preferably 0.
. 1 to 8 hours, particularly preferably 0.1 to 6 hours.
-Hydrogenation The cyclic olefin resin (A) according to the present invention has a structural unit represented by the formula (1), and X in the formula (1) is -CH = CH- or -CH _2. Represents CH ₂ —, and a plurality of X may be the same or different. That is, the cyclic olefin resin (A) used in the present invention may be a (co) polymer obtained by (co) polymerizing a cyclic olefin monomer capable of forming the cyclic olefin resin, and further hydrogenated. May be. The (co) polymer obtained by (co) polymerizing a cyclic olefin monomer is in the state of an olefinically unsaturated group where X is represented by —CH═CH—. From the viewpoint of heat resistance stability, It is preferable that such an unsaturated group is hydrogenated so that the X is converted into a group represented by —CH ₂ CH ₂ —, and the total of X in the structural unit (1) (2 types) In the case of the resin having the structural unit represented by the above formula (1), the total of X each of which is 100 mol%, usually 80 mol% or more, preferably 85 mol% or more, more preferably 90 mol% or more, Particularly preferably, 95 mol% or more is —CH ₂ C.
H ₂ − is desirable. The higher the ratio of X being —CH ₂ CH ₂ —, that is, the higher the hydrogen conversion rate of the (co) polymer, the more stable (co) polymer is obtained, and coloration and deterioration due to heat are suppressed. However, the hydrogenated product referred to in the present invention is a product obtained by hydrogenating the olefinically unsaturated group generated by ring-opening (co) polymerization, and an aromatic ring skeleton such as a benzene ring derived from a monomer structure. The conjugated double bond in the ring is preferably not substantially hydrogenated.

  The hydrogenation reaction is desirably carried out under the condition that the intracyclic conjugated double bond in the aromatic ring skeleton is not substantially hydrogenated. For example, a hydrogenation reaction catalyst is added to a ring-opening (co) polymer solution, and hydrogen gas at normal pressure to 300 atm, preferably 3 to 200 atm, is added to the solution. , Preferably it can carry out by making it react at 50-200 degreeC. The reaction time is 0.1 to 10 hours, preferably 0.1 to 8 hours, more preferably 0.1 to 6 hours after reaching the reaction temperature.

  As the hydrogenation reaction catalyst, those used for the usual hydrogenation reaction of olefinic compounds can be used, and heterogeneous catalysts and homogeneous catalysts are known. Examples of the heterogeneous catalyst include a solid catalyst in which a noble metal catalyst material such as palladium, platinum, nickel, rhodium, and ruthenium is supported on a carrier such as carbon, silica, alumina, and titania. Examples of homogeneous catalysts include nickel naphthenate / triethylaluminum, nickel acetylacetonate / triethylaluminum, cobalt octenoate / n-butyllithium, titanocene dichloride / diethylaluminum monochloride, rhodium acetate, chlorotris (triphenylphosphine) rhodium. Dichlorotris (triphenylphosphine) ruthenium, chlorohydrocarbonyltris (triphenylphosphine) ruthenium, dichlorocarbonyltris (triphenylphosphine) ruthenium, and the like. These catalysts may be in the form of powder or granules. In addition, this hydrogenation reaction catalyst can be used singly or in combination of two or more.

It is necessary to adjust the amount of these hydrogenation reaction catalysts in order to prevent the conjugated double bond in the ring in the aromatic ring skeleton from being substantially hydrogenated. The weight ratio of “combination: hydrogenation reaction catalyst” is usually used at a ratio of 1: 1 × 10 ⁻⁶ to 1: 2.

Imide bond-containing compound (B)
The imide bond-containing compound (B) used in the present invention contains one or more selected from the group consisting of the polymer (2-1), the compound (2-2) and the compound (2-3).

Of these, the polymer (2-1) is usually a condensation reaction of a tetracarboxylic dianhydride and a diamine, and the compound (2-2) is a condensation reaction of a tetracarboxylic dianhydride and a monoamine, a compound (2 -3) can be synthesized by a condensation reaction between a diamine and a cyclic dicarboxylic acid anhydride.

・ Polymer (2-1)
The polymer (2-1) is obtained by reacting tetracarboxylic dianhydride and diamine to synthesize a polyamic acid, and imidizing the polyamic acid. Examples of tetracarboxylic dianhydrides and diamines that can form such a structure are shown below.

-Tetracarboxylic acid dianhydride Examples of the tetracarboxylic acid dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,2-dimethyl-1,2,3,4-cyclobutanetetra. Carboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3
-Dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2, 3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ′, 4,4′-dicyclohexyltetracarboxylic dianhydride, 2,3 , 5-tricarboxycyclopentylacetic acid dianhydride, 2,3,5,6-norbornanetetracarboxylic dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,
5-tetrahydrofurantetracarboxylic dianhydride, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 4- (2 , 5-Dioxotetrahydrofuran-3-yl) -7-methyl-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 1,3,3a, 4,5,9b-hexahydro- 5 (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 5- (2,5-dioxotetrahydrofural)-
3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2,2,2
] -Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, spiro [2,5-dioxotetrahydrofuran-3,6'-bicyclo [2.3.1] heptane-3- Oxa-2,4-dione], butanetetracarboxylic dianhydride,
Pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic dianhydride, 1,4,5, 8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ', 4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4 ′
-Bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-isopropylidene diphthalic dianhydride, 3,3', 4,4'-perfluoroisopropylidene Dendiphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride,
Bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid)- 4,4′-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4′-diphenylmethane dianhydride, ethylene glycol-bis (anhydro trimellitate), propylene glycol-bis (anhydro trimellitate) ) 1,4-butanediol-bis (anhydrotrimellitate), 1,6-hexanediol-bis (anhydrotrimellitate), 1,8-octanediol-bis (anhydrotrimellitate), 2,2-bis (4-hydroxyphenyl) propane-bis (anhydrotrimellitate) and the like That.

Preferably, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclo Pentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride,
3,3 ′, 4,4′-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 2,3,5,6-norbornanetetracarboxylic dianhydride, 2, 3,4,5-tetrahydrofurantetracarboxylic dianhydride, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 4- (2,5-dioxotetrahydrofuran-3-yl) -7-methyl-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 1,3,3a, 4,5, 9b-Hexahydro-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 5- (2,5-dioxotetrahydrofural) -3 -Methyl-3-cyclo Hexene-1,2-dicarboxylic dianhydride, bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, spiro [2,5-dioxo Tetrahydrofuran-3,6′-bicyclo [2.3.1] heptane-3-oxa-2,4-dione], butanetetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ′, 4, 4'-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyl ether tetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride 3,3 ′, 4,4′-isopropylidenediphthalic dianhydride, 3,3 ′, 4,4′-perfluoroisopropylidenediphthalic dianhydride, 3,3 ′, 4,4 ′ -Biphenyltetracarboxylic dianhydride.

Tetracarboxylic dianhydride can be used alone or in combination of two or more.
-Diamine As the diamine, for example, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-bis (4-aminophenoxy) Biphenyl, p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylsulfone, 4,4 '-Diaminobenzanilide, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 5-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 6-amino-1- (4′-aminophenyl) -1,3,3-trimethylindane, 3,4′-diaminodiphenyl ether, 3,3′-diaminobenzophenone, 3, '- diaminobenzophenone, 4,
4′-diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis ( 4-aminophenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl]
Sulfone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-amino) Phenyl) -10-hydroanthracene, 2,7-diaminofluorene, 9,9-bis (4-aminophenyl) fluorene, 4,4′-methylene-bis (2-chloroaniline), 2,2 ′, 5, 5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl 4,4 ′-(p-phenyleneisopropylidene) bisaniline, 4,4 ′-(m-phenyleneisopropylidene) bisaniline, 2,2′-bis [4- (4-amino-2-trifluoromethylphenoxy) Fe Nyl] hexafluoropropane, 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 4,4′-diamino-2,2′-dimethylbiphenyl, 4,4′-bis [(4 -Amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl, 1,1-metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylene Diamine, Nonamethylenediamine, 4,4-Diaminoheptamethylenediamine, 1,4-Cyclohexanediamine, Isophoronediamine, Tetrahydrodicyclopentadienylenediamine, Hexahydro-4,7-methanoindanylenediethylenediamine, Tricyclo [6 .2.1.0 ^2,7] - Undeshirenjime Diamine, 4,4'-methylenebis (cyclohexylamine), 2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2,3 -Dicyanopyrazine, 5,6-diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis (3-aminopropyl) piperazine, 2, , 4-diamino-6-isopropoxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6-phenyl-1,3, 5-triazine, 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-1,3,5-triazine, 4,6-diamino-2-vinyl-s-triazine, 2,4- Diamino-5-pheny Thiazole, 2,6-diaminopurine, 5,6-diamino-1,3-dimethyl uracil, 3,5-diamino-1,2,4
Triazole, 6,9-diamino-2-ethoxyacridine lactate, 3,8-diamino-6-phenylphenanthridine, 1,4-diaminopiperazine, 3,6-diaminoacridine, bis (4-aminophenyl) phenylamine 2,2-bis (4-aminocyclohexyl) hexafluoropropane, 2,2′-dimethyl-4,4′-diaminobicyclohexyl, 3,3′-dimethyl-4,4′-diaminobicyclohexyl, 2, 2'-ditrifluoromethyl-4,4'-diaminobicyclohexyl, 3,3'-ditrifluoromethyl-4,4'-diaminobicyclohexyl and a compound represented by the following general formula (i) or (ii):

(In formula (i), R ¹⁵ represents a monovalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and piperazine, and Z represents a divalent organic group.)

(In the formula (ii), R ¹⁶ represents a divalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and piperazine, Z represents a divalent organic group, The existing X may be the same or different.)
Monosubstituted phenylenediamines represented by the following formula (iii):

(In the formula (iii), R ¹⁷ represents —O—, —COO—, —OCO—, —NHCO—, —CONH.
-Represents a divalent organic group selected from -CO-, and R ¹⁸ represents a monovalent organic group having a steroid skeleton, a monovalent organic group having a trifluoromethyl group or a fluoro group, or a carbon number of 6 to 30 alkyl groups are shown. )
Diaminoorganosiloxane represented by the following formula (iv):

(In formula (iv), R ¹⁹ each independently represents a hydrocarbon group having 1 to 12 carbon atoms, q is an integer of 1 to 20, and r is an integer of 1 to 3).
Examples thereof include compounds represented by the following formulas (v) to (ix).

(In the above formula (viii), t is an integer of 2 to 12.)

(In the above formula (ix), u is an integer of 1 to 5.)
The said diamine compound can be used individually or in combination of 2 or more types. Among these, diamine having a biphenyl skeleton, p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,7-diaminofluorene, 4,4 ′ -Diaminodiphenyl ether, 2,2-
Bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2 -Bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '-(p-phenylenediisopropylidene) bisaniline, 4,4'-(m-phenylenedi Isopropylidene) bisaniline, 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 4,4′-diamino-2,2′-dimethylbiphenyl, 1,4-cyclohexanediamine, 4,4 '-Methylenebis (cyclohexylamine), 1,4-bis (4-aminophenoxy) benzene, 4,4
'-Methylenebis (cyclohexylamine), 2,2-bis (4-aminocyclohexyl) hexafluoropropane, 2,2'-dimethyl-4,4'-diaminobicyclohexyl, 3,3'-dimethyl-4,4' -Diaminobicyclohexyl, 2,2'-ditrifluoromethyl-4,4'-diaminobicyclohexyl, 3,3'-ditrifluoromethyl-4,4'-diaminobicyclohexyl, the above formulas (v) to (ix) (B) component represented by 6
-Diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-
Diaminoacridine, a compound represented by the following formula (i-1) among the compounds represented by the above formula (i), and a compound represented by the following formula (ii-1) among the compounds represented by the above formula (ii) Of the compounds represented by formula (iii) and the compounds represented by formula (iii), compounds represented by the following formulas (iii-1) to (iii-6) are preferred.

Reaction of tetracarboxylic dianhydride and diamine The reaction of tetracarboxylic anhydride and diamine is obtained by reacting tetracarboxylic anhydride and diamine with tetracarboxylic anhydride relative to 1 equivalent of amino group contained in diamine. The acid anhydride group contained in the product is used in a ratio of 0.2 to 2 equivalents, and is usually performed at a temperature of 0 to 150 ° C, preferably 0 to 100 ° C in an organic solvent.

The organic solvent is not particularly limited as long as it can dissolve the acid anhydride and diamine which are reaction raw materials and the polyamic acid which is a polymer to be generated. Specifically, γ-butyrolactone, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-
Aprotic polar solvents such as dimethylacetamide, dimethylsulfoxide, tetramethylurea, hexamethylphosphotriamide; phenolic solvents such as m-cresol, xylenol, phenol, halogenated phenol, carboxylic acid solvents such as acetic acid, etc. be able to.

  The amount of the organic solvent used is preferably such that the total amount of the acid anhydride and diamine, which are reaction raw materials, is 0.1 to 30% by weight based on the total amount of the reaction solution. In addition, polyamic acid that produces alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, etc., which are poor solvents for the polyamic acid produced, does not precipitate in the organic solvent. You may use together in the range.

  The polyamic acid obtained as described above is imidized by heating, or imidized in the presence of a dehydrating agent and an imidization catalyst to cause dehydration and ring closure, thereby obtaining the polyimide. The temperature in the imidization treatment by heating is usually 60 to 250 ° C, preferably 100 to 170 ° C.

  Examples of the dehydrating agent include acetic acid, acetic anhydride, propionic anhydride, trifluoroacetic anhydride, and the like. The amount of the dehydrating agent used is preferably 1.6 to 20 mol with respect to 1 mol of the polyamic acid repeating unit.

  Examples of the imidization catalyst include tertiary amines such as pyridine, collidine, lutidine, and triethylamine, but are not limited thereto. The ratio of the imidization catalyst used is preferably 0.5 to 10 mol with respect to 1 mol of the dehydrating agent used. In addition, as an organic solvent used for this imidation process, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid can be mentioned. And the temperature in this imidation process is 0-180 degreeC normally, Preferably it is 60-150 degreeC.

  The polyimide used in the present invention may be a partially imidized polymer in which the polyamic acid is not 100% imidized, but the imidization ratio is preferably 50% or more, more preferably 80% or more, particularly Preferably it is 90% or more, Most preferably, it is 95% or more. By making the imidation ratio in the above range, the controllability of the retardation of the cyclic olefin resin composition film of the present invention is improved, which is preferable.

Compound (2-2)
Compound (2-2) can be obtained by reacting tetracarboxylic dianhydride and monoamine to synthesize an amic acid compound and imidizing the amic acid. Examples of the tetracarboxylic dianhydride that can form such a structure include those exemplified as the tetracarboxylic dianhydride that can form the polymer (2-1). In addition, examples of the monoamine include those having the same skeleton as that exemplified as the diamine capable of forming the polymer (2-1) and having one amino group.

  As the conditions for producing the compound (2-2), the solvents, temperatures, dehydrating agents, catalysts, etc. exemplified as the production conditions for the polymer (2-1) can be used, but are included in the tetracarboxylic acid anhydride. It is preferable that the amino group contained in the monoamine is used in a ratio of 0.5 to 1.5 equivalents per 1 equivalent of the acid anhydride group.

・ Compound (2-3)
The compound (2-3) is obtained by reacting a diamine and a cyclic dicarboxylic acid anhydride to synthesize an amic acid compound and imidizing the amic acid compound. Examples of the diamine that can form such a structure include the same diamines as those exemplified as the diamine that can form the polymer (2-1). In addition, examples of the cyclic dicarboxylic acid anhydride include those having a skeleton similar to those exemplified as the tetracarboxylic dianhydride capable of forming the polymer (2-1) and having one carboxylic acid anhydride group. it can. As the conditions for producing such a compound (2-3), the solvent, temperature, dehydrating agent, catalyst and the like exemplified as the production conditions for the polymer (2-1) can be used. It is preferable to use the acid anhydride group contained in the dicarboxylic acid anhydride at a ratio of 0.5 to 1.5 equivalents per 1 equivalent of the group.

Using an Ubbelohde viscometer of the imide bond-containing compound (B) used in the present invention, N-
The logarithmic viscosity measured at a sample concentration of 0.5 g / dL and a temperature of 30 ° C. in methyl pyrrolidone is usually 0.01 to 1.00, preferably 0.01 to 0.90, more preferably 0.01 to 0.00. 80. When the solution viscosity is within the above-described range, it is possible to maintain controllability of the retardation value and its wavelength dispersion and to ensure high compatibility with the cyclic olefin resin (A).

Resin Composition The resin composition according to the present invention contains the above-mentioned cyclic olefin resin (A) and the imide bond-containing compound (B).

  The ratio (mixing ratio) between the cyclic olefin resin (A) and the imide bond-containing compound (B) in the resin composition is a weight ratio ((A) / (B)), preferably 99/1 to 50. / 50, more preferably in the range of 99/1 to 70/30. When the composition ratio is within such a range, the transparency, strength, and retardation of the molded product obtained from the resin composition of the present invention and the controllability of the wavelength dispersion are high. The resin composition can be prepared by a known method.

<Molding>
The resin composition of the present invention can be suitably molded into a desired shape by any of melt molding such as extrusion molding and injection molding and molding by a solution casting method (cast method).

  The physical property value of the resin composition of the present invention is the copolymer composition ratio of each component of the cyclic olefin resin (A) and the imide bond-containing compound (B) constituting the resin composition and the amount of the molecular weight regulator used. The amount of each component used can be controlled, but various additives may be added and adjusted within a range not losing the characteristics of the resin composition of the present invention. Moreover, well-known various additives can be added to the cyclic olefin ring-opening polymer of the present invention for other purposes.

Examples of the additive include 2,6-di-t-butyl-4-methylphenol and 2,2 ′.
-Methylenebis (4-ethyl-6-tert-butylphenol), 2,5-di-tert-butylhydroquinone, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-
Hydroxyphenyl) propionate], 4,4'-thiobis- (6-tert-butyl-3-methylphenol), 1,1-bis (4-hydroxyphenyl) cyclohexane, octadecyl 3- (3,5-di -T-butyl-4-hydroxyphenyl) propionate, 3,3 ', 3 ", 5,5', 5" -hexa-t-butyl-a, a ', a "-(mesitylene-2,4,6 -Triyl) phenol-based, hydroquinone-based antioxidants such as tri-p-cresol; tris (4-methoxy-3,5-diphenyl) phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-) Phosphorus antioxidants such as t-butylphenyl) phosphite, etc. By adding one or more of these antioxidants, the oxidation resistance of the ring-opening copolymer can be improved. For example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- Light resistance can also be improved by adding an ultraviolet absorber such as [(2H-benzotriazol-2-yl) phenol], etc. Furthermore, additives such as lubricants are added for the purpose of improving processability. These additives can be used singly or in combination of two or more.

  Moreover, the resin composition of this invention is a range which does not impair the objective of this invention, As a resin component, well-known resin other than components (A) and (B), such as cyclic olefin resin other than a component (A), is used. It can also be included.

  The resin composition of the present invention can be molded into a desired shape, but is excellent in optical characteristics, and thus is useful for various optical materials. Especially, shaping | molding into a film or a sheet | seat (in this invention, these are named generically and a film) is preferable, and can use it suitably for an optical film and its use. Moreover, the resin composition of the present invention is also suitable for use in producing optical materials such as various lenses by injection molding.

- an optical film resin composition of the present invention, the structure described above, the kind of the substituent R ¹ to R ¹⁰ in the formula (1) of the cyclic olefin resin (A), the backbone and substituent of the imide bond-containing compound (B) By setting the structure / type, copolymer composition ratio, and mixing ratio of components (A) and (B), the wavelength dependence of the absolute value and retardation of the birefringence of molded products such as films obtained Can be prepared. Moreover, the polymer film etc. which were shape | molded from the resin composition obtained also when the resin composition of this invention contains well-known cyclic olefin resin other than a component (A) and (B) as a resin component, etc. It is possible to adjust the wavelength dependence of the birefringence value, the absolute value of the birefringence, and the phase difference.

  By selecting and using the resin composition of the present invention, it is possible to easily control the positive / negative of the birefringence value, the magnitude of the absolute value, the magnitude of the wavelength dependence of the phase difference, and the like, and thus obtained from the resin composition of the present invention. The obtained film can be suitably used as an optical compensation film. For this reason, it is preferable that the resin composition of the present invention or a composition containing the same is formed into an optical film by casting or extrusion. Furthermore, since the optical film exhibits its performance sufficiently by stretching, a free-width uniaxial stretching, a width-constrained uniaxial stretching, a sequential biaxial stretching, a simultaneous biaxial stretching, or a shrink film is applied during or after stretching. It is preferable to make a stretched film by so-called Z-axis orientation (Z-axis stretching) for adjusting the refractive index in the film thickness direction. The film can be suitably stretched by heat stretching.

  Since the optical film of the present invention exhibits excellent transparency in a film formed by extrusion molding or cast molding, it can be suitably used as various protective films. In addition, a stretched film obtained by further stretching a film obtained by forming a film can be suitably used as a film constituting a retardation plate or a liquid crystal display device because it exhibits unique wavelength dependency.

  A film obtained by stretching an optical film obtained by forming a film from the resin composition of the present invention selects the type and composition ratio of the component (A) and the component (B) constituting the resin composition. Thus, in the visible light region, a film having positive wavelength dispersibility in which the phase difference Re increases as the transmitted wavelength decreases, and the dispersibility is a conventionally known cyclic olefin ring-opening (co) polymer. It is bigger than a film made of Such a film can be suitably used as a retardation film. Such a film is suitable as a film constituting a polarizing plate or a liquid crystal display device.

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples. In the following, “parts” and “%” mean “parts by weight” and “% by weight” unless otherwise specified. Moreover, room temperature is 25 degreeC.

The measuring method of various physical property values in the present invention is shown below.
・ Glass transition temperature (Tg)
Using a differential scanning calorimeter (trade name: DSC6200, manufactured by Seiko Instruments Inc.), an extrapolated glass transition start temperature was determined according to Japanese Industrial Standard K7121. Hereinafter, it is simply referred to as glass transition temperature (Tg).

-Weight average molecular weight and molecular weight distribution Gel permeation chromatography (HLC-8220GPC, manufactured by Tosoh Corp., column; Guard column H _XL -H, TSK gel G7000H _XL , TSK gel GMH _XL 2 units, TSK gel manufactured by Tosoh Corp.) G2000H _XL sequentially connected, solvent: tetrahydrofuran, flow rate: 1 mL / min, sample concentration 0.7-0.8 wt%, injection volume: 70 μL, measurement temperature: 40 ° C., detector: RI (40 ° C.), standard substance: Tosoh Corporation ) TSK standard polystyrene) and the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were measured. The Mn is a number average molecular weight.

・ Evaluation of retardation and birefringence A toluene or methylene chloride solution of a ring-opening polymer (concentration: 25%) was cast on a smooth glass plate, dried, and then 100 μm thick and 0.5 to 0.8% residual solvent. A colorless and transparent film was obtained. The film was uniaxially stretched 1.2 to 2.0 times at a temperature 5 to 10 ° C. higher than the glass transition temperature (Tg) of the film. The retardation and birefringence values of the stretched film were measured using a retardation measuring device (manufactured by Oji Scientific Instruments, trade name: KOBRA21DH).

-Logarithmic viscosity Using a Ubbelohde viscometer, the sample concentration in chloroform is 0.5 g / dL, and the temperature is 30.
Measured at ° C.
Synthesis Example 1 (Synthesis Example of Cyclic Olefin Resin (A))
As a monomer, 8-methoxycarbonyl-8-methyltetracyclo represented by the following formula (1a) [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 50 g, 1-hexene 3.6 g as a molecular weight regulator, and toluene 100 g were charged into a nitrogen-substituted reaction vessel and heated to 80 ° C. To this was added 0.09 mL of a toluene solution of triethylaluminum (0.6 mol / L) and 0.29 ml of a methanol-modified WCl ₆ toluene solution (0.025 mol / L), and the mixture was reacted at 80 ° C. for 3 hours to open the ring. A polymer was obtained. Next, 0.02 g of RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ as a hydrogenation reaction catalyst is added, the hydrogen gas pressure is adjusted to 9 to 10 MPa, and the reaction is performed at a temperature of 160 to 165 ° C. for 3 hours. I let you. After completion of the reaction, the resulting product was precipitated in a large amount of methanol to obtain a hydrogenated product [glass transition temperature (Tg) = 167 ° C., weight average molecular weight (Mw) = 5.6 × 10 ⁴ , molecular weight distribution. (Mw
/Mn)=3.2, yield 45 g (90% yield)]. The hydrogenation rate of this hydrogenated product determined by NMR measurement was 99.0% or more. Hereinafter, the obtained ring-opened polymer hydrogenated product is referred to as polymer 1b.

Synthesis Example 2 (Synthesis example of imide bond-containing compound (B))
3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (5 g) and p-phenoxyaniline (6.3 g) were dissolved in 100 mL of acetic acid, reacted at 135 ° C for 8 hours, washed and purified with a large amount of methanol. Then, a white solid imide bond-containing compound 2a represented by the following formula (2a) was obtained by drying with a vacuum dryer. The weight average molecular weight (Mw) was 410.

[Example 1]
3 g of the cyclic olefin ring-opening polymer 1b obtained in Synthesis Example 1 and 0.075 g of the imide compound 2a obtained in Synthesis Example 2 were dissolved in 50 g of methylene chloride and cast into a smooth glass bathtub. The film was peeled from the bathtub and then dried for 12 hours with a vacuum dryer at 100 ° C. to obtain a film having a thickness of 140 μm.

Next, this film was cut into a width of 10 × 70 mm, and stretched by heating with a tensile tester equipped with a thermostatic bath to prepare a stretched film. When the film was stretched twice at a rate of 220% / min at 180 ° C., a stretched film having a film thickness of 93 μm was obtained, and the phase difference was measured to be R480 = 407, R550 = 401, R750 = 393 nm. Here, R480, R550, and R750 represent phase differences at wavelengths of 480, 550, and 750 nm, respectively.

[Example 2]
3 g of the cyclic olefin ring-opening polymer 1b obtained in Synthesis Example 1 and 0.15 g of the imide compound 2a obtained in Synthesis Example 2 were dissolved in 50 g of methylene chloride and cast into a smooth glass bathtub. The film was peeled from the bathtub and then dried for 12 hours with a vacuum dryer at 100 ° C. to obtain a film having a thickness of 140 μm.

  Next, this film was cut into a width of 10 × 70 mm, and stretched by heating with a tensile tester equipped with a thermostatic bath to prepare a stretched film. When the film was stretched twice at a rate of 220% / min at 180 ° C., a stretched film having a film thickness of 93 μm was obtained, and the phase difference was measured to be R480 = 391, R550 = 381, and R750 = 374 nm.

[Comparative Example 1]
3 g of the cyclic olefin ring-opening polymer 1b obtained in Synthesis Example 1 was dissolved in 50 g of methylene chloride and cast into a smooth glass bathtub. This film was peeled from the bathtub and then dried for 12 hours with a vacuum dryer at 100 ° C. to obtain a film having a thickness of 135 μm.

  Next, this film was cut into a width of 10 × 70 mm, and stretched by heating with a tensile tester equipped with a thermostatic bath to prepare a stretched film. When the film was stretched twice at a rate of 220% / min at 180 ° C., a stretched film having a film thickness of 90 μm was obtained, and the phase difference was measured to be R480 = 370, R550 = 368, and R750 = 365 nm.

  The results of these examples and comparative examples are shown in Table 1, and the difference in wavelength dispersibility of the stretched films obtained in each of the examples and comparative examples is shown in FIG.

  From these results, it has been clarified that the wavelength dispersion is remarkably increased in the example with respect to the comparative example. Further, it has been found that the changing ratio can be achieved by changing the composition ratio of the resin composition of the present invention in accordance with the purpose. That is, in the present invention, it has been confirmed that a resin composition can be obtained in which the wavelength dispersibility can be easily controlled while maintaining the high heat resistance which is one of the characteristics of the cyclic olefin ring-opening (co) polymer. It was.

  The resin composition of the present invention is suitably used as a raw material for various optical films and optical materials. The film according to the present invention is particularly suitable for optical applications such as various protective films as an unstretched film, and the stretched film can be a retardation film exhibiting a desired reverse wavelength dispersibility. Various liquid crystal display elements such as mobile phones, digital information terminals, pagers, navigation, in-vehicle liquid crystal displays, liquid crystal monitors, light control panels, displays for OA equipment, displays for AV equipment, and electroluminescence displays It can be used for an element or a touch panel. The optical component according to the present invention is suitable as various optical members obtained by injection molding, such as various optical lenses and optical disks.

FIG. 1 is a graph showing the wavelength dispersibility of stretched films obtained in Examples 1 and 2 and Comparative Example 1.

Claims (7)

(A) a cyclic olefin resin having a structural unit represented by the following formula (1);
(B) the following formula (2-2) or the following formula (2-3) to contain the one or more imide bond-containing compound selected from the group consisting of compounds represented by the resin composition for an optical film, wherein object.

In formula (1), a and b are independently 0 or 1, and c and d are independently an integer of 0 to 2. X is a group represented by the formula: —CH═CH— or a group represented by the formula: —CH ₂ CH ₂ —. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are each independently a hydrogen atom; a halogen atom; an oxygen atom, a sulfur atom, a nitrogen atom, Or a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms which may have a linking group containing a silicon atom; or a polar group. R ⁷ and R ⁸ , or R ⁹ and R ¹⁰ may be integrated to form a divalent hydrocarbon group, and R ⁷ or R ⁸ and R ⁹ or R ¹⁰ are bonded to each other, And a carbon atom to which is bonded to form a carbocycle or a heterocycle (these carbocycles or heterocycles may be monocyclic structures or other rings may be condensed to form a polycyclic structure). May be. )

(In Formula (2-2) and Formula (2-3), A represents a tetravalent organic group, B, R ¹³ , and R ¹⁴ each independently represent a divalent organic group, R ¹¹ and R ¹² each independently represents a monovalent organic group.) The cyclic olefin resin (A) is 90 mol% of structural units in which X in the formula (1) is a group represented by —CH ₂ CH ₂ — among the structural units represented by the formula (1). The resin composition for optical films according to claim 1, comprising the above. The ratio ((A) / (B)) between the cyclic olefin-based resin (A) and the imide bond-containing compound (B) is in a range of 99/1 to 50/50 by weight. Item 3. The resin composition for an optical film according to Item 1 or 2. A film obtained by forming the resin composition for an optical film according to claim 1 into a film by a casting method or an extrusion method. A stretched film obtained by forming the resin composition for an optical film according to any one of claims 1 to 3 into a film by a casting method or an extrusion method, and heating and stretching. A polarizing plate comprising a stretched film comprising the resin composition for an optical film according to claim 1. The liquid crystal display device characterized by including the stretched film which consists of the resin composition for optical films in any one of Claims 1-3.

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